Semiconductor device and method of manufacturing the same

ABSTRACT

A semiconductor device comprising a substrate and a ferroelectric capacitor formed on the substrate. The ferroelectric capacitor includes a lower electrode, an upper electrode and a ferroelectric film interposed between the lower and upper electrodes. The ferroelectric capacitor having sidewalls receded from sidewalls of the upper electrode.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of and claims the benefit of priorityunder 35 U.S.C. §120 from U.S. application Ser. No. 11/385,999, filedMar. 22, 2006, and claims the benefit of priority under 35 U.S.C. §119from Japanese Patent Application No. 2005-264995, filed Sep. 13, 2005,the entire contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a semiconductor device havingferroelectric capacitors, such as a ferroelectric random access memory(FeRAM) or a micro-electrical mechanical system (MEMS), and a method ofmanufacturing the semiconductor device

2. Description of the Related Art

In recent years, the integration density of dynamic random accessmemories (DRAMs) has increased. As the integration density increases,the capacitance of each element is approaching its lower limit (i.e.,the smallest capacitance below which the element can no longer operate).Hence, nonvolatile semiconductor memories having ferroelectriccapacitors, such as FeRAMs, are being developed as devices in whichelements can operate even at a smaller capacitance. To manufacture asemiconductor memory of this type, ferroelectric capacitors must beformed at a time by using one mask (1PEP) to raise the integrationdensity.

However, the material used for the electrodes of the ferroelectriccapacitor, particularly precious metal (Pt or Ir), is far less volatilethan is desired. Consequently, metal residue may lie between the upperand lower electrodes of each capacitor if the capacitors are formed at atime by means of reactive ion etching (RIE). The metal residue willinduce capacitor leakage, which increases defective bits or defectivechips in numbers. Thus, the metal residue will lower the manufactureyield of the products.

In manufacturing a FeRAM having ferroelectric capacitors, metal residueis formed when ferroelectric capacitors are formed at a time, eachcomprising a lower electrode, a ferroelectric layer and an upper layer.The metal residue induces capacitor leakage, which increases defectivebits or defective chips in numbers. This problem is not limited tononvolatile semiconductor memories such as FeRAMs. Rather, the problemmay arise in various semiconductor devices that comprise ferroelectriccapacitors.

BRIEF SUMMARY OF THE INVENTION

According to an aspect of this invention, there is provided asemiconductor device, comprising:

a substrate; and

a ferroelectric capacitor formed on the substrate, comprising a lowerelectrode, an upper electrode and a ferroelectric film interposedbetween the lower and upper electrodes, and having sidewalls recededfrom sidewalls of the upper electrode.

According to another aspect of this invention, there is provided asemiconductor device, comprising:

a substrate; and

a ferroelectric capacitor provided on the substrate and fabricated byforming a lower electrode, a ferroelectric film and a mask-material filmon a part of the substrate, by making an opening in the mask-materialfilm and by burying the upper electrode in the opening.

According to still another aspect of this invention, there is provided asemiconductor device, comprising:

a substrate;

a ferroelectric capacitor provided on the substrate and comprising alower electrode, an upper electrode and a ferroelectric film interposedbetween the upper and lower electrodes, the upper electrode beingprovided in a region inner of a peripheral region of the ferroelectricfilm; and

a mask-material film provided on the ferroelectric film and surroundingthe peripheral region of the upper electrode.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

FIG. 1 is a sectional view showing FeRAM cell according to a firstembodiment of the present invention;

FIGS. 2A to 2C are sectional views explaining a method of manufacturingFeRAM according to the first embodiment of the invention;

FIG. 3 is a diagram representing the relation between the concave depthd of the ferroelectric layer and the capacitor leakage current;

FIG. 4 is a diagram representing the relation between the concave depthd of the ferroelectric layer and the degree of capacitor polarization;

FIG. 5 is a sectional view showing the structure of an unfinished FeRAMthat has metal wiring;

FIG. 6 is a sectional view depicting the structure of FeRAM cellaccording to a second embodiment of this invention;

FIGS. 7A and 7B are sectional views explaining steps of manufacturingFeRAM according to the second embodiment of the invention; and

FIG. 8 is a sectional view showing a modification of the secondembodiment of this invention.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the present invention will be described, thus explainingthe invention in detail.

First Embodiment

FIG. 1 is a sectional view showing FeRAM cell according to the firstembodiment of this invention.

As FIG. 1 shows, a gate insulating film 21 is provided on Si substrate10, and a gate electrode 22 is provided on the gate insulating film 21.Using the gate electrode 22 as mask, a source region 23 and a drainregion 24 are formed. Thus, the film 21, electrode 22 and regions 23 and24 constitute a switching transistor 20.

An interlayer insulating film 11 is provided on the substrate 10 andcovers the transistor 20. A plug electrode 12 is buried in theinterlayer insulating film 11. The plug electrode 12 therefore connectsthe drain region 24 of the transistor 20 to the interlayer insulatingfilm 11. On a part of the interlayer insulating film 11 there isprovided a ferroelectric capacitor 30 that contacts the plug electrode12. The capacitor 30 comprises a lower electrode 31, a ferroelectricfilm 32 and an upper electrode 33. The lower electrode 31 is a TiAlNlayer or a Ti/Ir/IrO₂/Ti/Pt/Ti layer. Nonetheless, the electrode 31shown in FIG. 1 is composed of Ti layer 31 a, Ir layer 31 b, IrO₂ layer31 c and Pt layer 31 d only. The ferroelectric film 32 is made of PZT.The upper electrode 33 is SrRuO₃/IrO₂ layer. Only the IrO₂ layer isshown in FIG. 1.

Note that the layers constituting the ferroelectric capacitor 30 havebeen formed by means of dry etching using a hard mask 41 made of SiO₂ orthe like. Metal residue 42 formed during the dry etching lie on thesidewalls of the ferroelectric capacitor 30.

The structure thus formed is identical in configuration to theconventional FeRAM cell. In the present embodiment, side etching isperformed on the ferroelectric film 32, receding the sidewalls of theferroelectric film 32. As the side etching proceeds, Metal residue 42 isremoved from the sidewalls of the ferroelectric film 32.

Namely, the embodiment is characterized in that the sidewalls of theferroelectric film 32 are concaved in the ferroelectric capacitor 30comprising the lower electrode 31, ferroelectric film 32 and upperelectrode 33. The residue 42 has been removed from the sides of theferroelectric capacitor film 32.

A method of manufacturing FeRAM according to the present embodiment willbe described below.

First, a switching transistor 20 was formed on an Si substrate 10 asshown in FIG. 2A. Then, an interlayer insulating film 11 was formed onthe substrate 10, covering the switching transistor 20. A plug electrode12 is formed in the interlayer insulating film 11. Thereafter, a lowerelectrode 31 made of TiAlN or composed of films 31 a to 31 d (i.e., fourfilms selected from Ti, Ir, IrO₂, Pt and SrRuO₃ films), a ferroelectriccapacitor film 32 (PZT), and an upper electrode 33 a (SrRuO₃/IrO₂) wereformed, one on another, on the interlayer insulating film 11.

Next, a hard mask 41 was formed on the upper electrode film 33 a asshown in FIG. 2B, in preparation for forming a capacitor.High-temperature etching was applied in this embodiment in order to formthe capacitor. The mask 41 was therefore SiO₂ film. Alternatively, itmay be SixNy film, SiO₂/Al₂O₃ film, an Al₂O₃ film or SiO₂/TiAlN/Al₂O₃film, or any combination of these films.

As shown in FIG. 2C, etching was performed on the upper electrode film33 a, ferroelectric film 32 and lower electrode films 31 a to 31 d, byusing the hard mask 41. A ferroelectric capacitor 30 was thereby formed,which comprised electrodes 31 and 33 and a ferroelectric film 32interposed between the electrodes 31 and 33. Residue 42 of Ir, i.e., amaterial of the electrodes, lay on the sidewalls of the capacitor 30 inmost cases. The residue 42 induced capacitor leakage, lowering the yieldof the product.

In order to remove the residue 42, isotropic etching was carried out inthe present embodiment. More precisely, dry etching was performed on thesidewalls of the ferroelectric capacitor 30, thereby removing the sourceof residue. The gas used in the isotropic etching was chlorine-basedgas, halogen-based gas, fluorine-based gas or reducing gas (e.g., Cl₂,BCl₃, CF₄, C₂F₆, C₄F₈, CHF₃ or CO). If the residue is of a large amount,the sidewalls of the ferroelectric capacitor should better be etchedwith a mixture of the above-mentioned gas and inert gas such as Ar,after the source of residue was removed to some extent. The CDE processmay be employed for this purpose. The method of removing the source ofresidue is not limited to these, nonetheless.

During this etching, the sidewalls of the ferroelectric film 32gradually receded, each coming to have a concave. As a result, thestructure shown in FIG. 1 was obtained.

The inventors hereof studied the relation between the capacitor leakagecurrent and the depth d of the concave made in the ferroelectric film32, i.e., the step width d at the sides of the upper electrode 33. Theresults were as shown in FIG. 3. As seen from FIG. 3, a concave havingdepth of 1 nm reduced the capacitor leakage current to 10⁻³ A/cm² orless. A concave having depth of 3 nm reduced the capacitor leakagecurrent to 10⁻⁶ A/cm² or less. Certainly, the absolute value of theleakage current depends on the capacitor material indeed. It is clear,however, that the concaves made in the sidewalls of the ferroelectriccapacitor can decrease the capacitor leakage.

Concaves can be made by various methods. Nonetheless, the capacitoracquired good characteristics when the concaves were made by theabove-mentioned dry etching or CDE process. The inventors studied therelation between the depth (step width d) of the concaves and the degreeof capacitor polarization. The results were as shown in FIG. 4. Asevident from FIG. 4, the capacitor was sharply degraded incharacteristics when the step width d exceeded 10% of the minimum size Tof the basic capacitor cell. (The capacitor was much degraded when thestep width was greater than 100 nm, i.e., 10% of TE=1×1 μm².) Hence, thestep width should be 10% of the minimum size T or less in order toreduce the leakage current and impart good polarization characteristicto the capacitor.

Thus, the present embodiment is characterized that the sidewall surfacesof the ferroelectric film 32 of the capacitor 30 recede inwards unlikethe sidewalls of the upper electrode 33. While etching is beingperformed on the sidewalls of the ferroelectric capacitor 30, not onlythe ferroelectric film 32, but also the upper electrode 33 may be partlyremoved in some cases. In view of this, it is sufficient for theferroelectric film 32 to be shorter than the upper electrode 33, asmeasured along a line perpendicular to the direction of thickness. Thatis, it suffices if the narrowest part of the ferroelectric film 32 is asmall width than the narrowest part of the upper electrode 33.

In FIG. 2, the sidewalls of the ferroelectric capacitor 30 areillustrated as if extending vertically as is desired. In practice, thesidewalls are tapered by 65 to 85° in most cases. If the sidewalls areso tapered, the description “the sidewall surfaces of the ferroelectricfilm 32 of the capacitor 30 recede inwards unlike the sidewalls of theupper electrode 33” means that the sidewall surfaces of theferroelectric film 32 do not lie on lines extending in the sidewallssurfaces of the upper electrode 33; they lie inside of these lines.

Next, a sidewall-protecting film was formed on the ferroelectriccapacitor 30 that had been etched at its sidewalls. More specifically,an Al₂O₃ film was deposited to a thickness of 10 to 50 nm by means ofALD process or sputtering process, or both. Alternatively, thesidewall-protecting film may be a ZrO₂ film, SiO₂ film, SixNy film orSiAlxOy film, or any combination of these films. After thesidewall-protecting film was so deposited, high-temperature annealingwas performed, successfully improving the polarization characteristic ofthe ferroelectric capacitor. This annealing is carried out, only ifnecessary. Note that the sidewall-protecting film can suppress thedamages to the interlayer insulating film 11.

FIG. 5 shows a ferroelectric memory according to this embodiment, thathad a metal wire formed in the step subsequent to the step of formingthe sidewall-protecting film. In FIG. 5, numeral 51 denotes thesidewall-protecting film, numeral 52 designates an electrode plug, andnumeral denotes the metal wire.

In the present embodiment, the ferroelectric film 32 of the capacitor 30is dry-etched at its sidewalls in the present embodiment. This preventsshort-circuiting between the lower electrode 31 and the upper electrode33 even if metal residue remains on the sidewalls of the ferroelectricfilm 32. Hence, metal residue 42, if any, would not degrade theferroelectric capacitor 30 even if the lower electrode 31, ferroelectricfilm 32 and upper electrode 33 are formed at a time. Thus, the capacitorleakage can be decreased, improving the characteristics of theferromagnetic capacitor 30.

Second Embodiment

FIG. 6 is a sectional view depicting the structure of FeRAM cellaccording to the second embodiment of the present invention. Thecomponents identical to those shown in FIG. 1 are designated at the samereference numerals and will not be described in detail.

As FIG. 5 depicts, a gate insulating film 21 is provided on Si substrate10, and a gate electrode 22 is provided on the gate insulating film 21.A source region 23 and a drain region 24 have been formed by using thegate electrode 22 as mask. Thus, the film 21, electrode 22 and regions23 and 24 constitute a switching transistor 20.

An interlayer insulating film 11 is provided on the substrate 10 andcovers the transistor 20. A plug electrode 12 is buried in theinterlayer insulating film 11. The plug electrode 12 therefore connectsthe drain region 24 of the transistor 20 to the interlayer insulatingfilm 11. On a part of the interlayer insulating film 11 there isprovided a ferroelectric capacitor 30 that contacts the plug electrode12. The capacitor 30 comprises a lower electrode 31, a ferroelectricfilm 32 and an upper electrode 35. The lower electrode 31 is a TiAlNlayer or a Ti/Ir/IrO₂/Ti/Pt/Ti layer. The electrode 31 shown in FIG. 1is, nonetheless, composed of Ti layer 31 a, Ir layer 31 b, IrO₂ layer 31c and Pt layer 31 d only. The ferroelectric film 32 is made of PZT. Theupper electrode 35 is SrRuO₃/IrO₂ layer. Only the IrO₂ layer is shown inFIG. 1.

Note that the lower electrode 31 and ferroelectric film 32 of theferroelectric capacitor 30 have been formed by means of dry etchingusing a hard mask 61 made of SiO₂ or the like. The mask 61 has anopening. The upper electrode 35 is formed in the opening of the mask 61.Etching residue 42 lies on the sidewalls of the ferroelectric capacitor30.

Thus, the second embodiment is characterized in that the upper electrode35 is formed in the opening of the mask 61, constituting theferroelectric capacitor 30, jointly with the lower electrode 31 and theferroelectric film 32. This configuration prevents the residue 42 on thesidewalls of the ferroelectric capacitor 30 from degrading thecharacteristics of the ferroelectric capacitor 30.

A method of manufacturing FeRAM according to the second embodiment willbe described, with reference to FIGS. 7A and 7B.

First, a switching transistor 20 is formed on Si substrate 10 as shownin FIG. 7A. Then, an interlayer insulating film 11 is formed on thesubstrate 10, covering the switching transistor 20. A plug electrode 12is formed in the interlayer insulating film 11. Thereafter, a lowerelectrode 31 made of TiAlN or composed of films 31 a to 31 d (i.e., fourfilms selected from Ti, Ir, IrO₂, Pt and SrRuO₃ films) and aferroelectric capacitor film 32 (PZT film) are formed, one on another,on the interlayer insulating film 11. Further, a hard mask (first mask)61 having a desired capacitor shape is formed on the ferroelectric film32. High-temperature etching is applied in the second embodiment inorder to form a capacitor. The first mask 61 is therefore an Al₂O₃ film.It may be instead SiO₂ film, SixNy film, SiO₂/Al₂O₃ film, Al₂O₃ film orSiO₂/TiAlN/Al₂O₃ film, or any combination of these films.

Preferably, the first mask 61 may be made of alumina (Al₂O₃), zirconiumoxide (ZrO₂), aluminum silicon oxide (AlSiO), silicon oxide (SiO₂),titanium oxide (TiO₂) or may be a multi-layer structure composed offilms of these oxides.

After the Al₂O₃ mask 61 is formed, the ferroelectric film 32 and thelower electrode films 31 a to 31 d are subjected to dry etching usingthe mask 61. If the taper angle is 70° or more, the residue of thelower-electrode material may lie on the sidewalls. At this stage,however, the upper electrode has yet to be formed, and such residue, ifany, would not result in capacitor leakage at all. After the dry etchingis performed, an Al₂O₃ film was deposited, as sidewall-protecting film51, to a thickness of 20 nm by means of ALD process or sputteringprocess, or both. The sidewall-protecting film 51 may instead be SixNyfilm, a ZrO₂ film or SiAlxOy film, or any combination of these films.The sidewall-protecting film 51 can suppress the damages to theinterlayer insulating film 11.

Then, an interlayer insulating film 55 is formed on thesidewall-protecting film 51. The interlayer insulating film 55 isprocessed, acquiring a flat surface. Further, a second mask 62 is formedon the interlayer insulating film 55. The second mask 62 has an openingsmaller than the ferroelectric capacitor that is to be fabricated. Ithas been formed by subjecting, for example, a resist film tophotolithography, thus making the opening in the resist film.

Next, RIE is carried out, using the second mask 62, making an opening inthe interlayer insulating film 55 and first mask 61, as is illustratedin FIG. 7B. In the step of making this opening, the etching can bereadily stopped at the Al₂O₃ mask, because SiO2, i.e., the material ofthe interlayer insulating film 55, and Al₂O₃, i.e., the material of thefirst mask 61, differ in etching rate. Thus, choline solution or thelike may be applied, making in the first mask 61 an opening that exposesthe ferroelectric film 32, after the etching is stopped for some time.Alternatively, RIE may be carried out, etching the interlayer insulatingfilm 55 and the first mask 61, one after the other, thereby making ahole that reaches the ferroelectric film 32.

After the second mask 62 is removed, an upper electrode 35, or SRO/IrO2electrode, is formed in the opening made in the interlayer insulatingfilm 55 and first mask 61, by means of CVD or sputtering. Then, CMP orthe like is performed, whereby the upper electrode 35 acquires a flatupper surface. Thereafter, on the interlayer insulating film 55, a wire53 is formed, which is connected to the upper electrode now provided atthe contact section. The structure shown in FIG. 6 is obtained.

That part of the ferroelectric film 32, which contacts the upperelectrode 36, is 1 nm or more thinner than the other part. The sidewallsof the lower electrode 31 and the sidewalls of the ferroelectric film 32lie on a line extending from the sidewall surfaces of the mask 61. Thatis, the sidewalls of the lower electrode 31 and the sidewalls of theferroelectric film 32 are flush with planes equivalent to the sidewallsurfaces of the mask 61. FIG. 6 shows an embodiment in which thesidewalls of the ferroelectric capacitor 30 are vertical as desired. Inpractice, however, the sidewalls are tapered by 65 to 85° in most cases.

The structure of FIG. 6 has been obtained by burying the upper-electrodematerial, by imparting a flat upper surface to the film of this materialand by forming a wire on the upper electrode formed at the contactsection. Instead, the upper-electrode material may be used to provide amain wire or a local wire, as is illustrated in FIG. 8. In this case, anupper electrode 36 is formed on the interlayer insulating film 55 and inthe opening of the first mask 61 and is patterned, proving a wire.

In the second embodiment, the upper electrode 35 and the ferroelectricfilm 32 are not processed at the same time. Rather, the upper electrode35 is formed, independently of the lower electrode 31 and ferroelectricfilm 32. More precisely, the upper electrode 35 is formed by fillingelectrically conductive material in the opening made in the mask 61after the ferroelectric film 32 and lower electrode 31 have beenprocessed by using the mask 61. This prevents short-circuiting betweenthe lower electrode 31 and the upper electrode 35 in spite of the metalresidue remains on the sidewalls of the ferroelectric film 32. Thus, thecapacitor leakage can be decreased, improving the characteristics of theferromagnetic capacitor 30. In addition, the number of PEPs used is justthe same as in the case where the ferroelectric film and upper electrodeare formed at a time.

Modified Embodiment

The present invention is not limited to the embodiments described above.In the first embodiment, etching is performed to remove the residue,after the etching is carried out to provide the ferroelectric capacitor.Nevertheless, the etching for removing the residue may be carried out atthe same time as the etching for providing the ferroelectric capacitor.Moreover, the materials of the ferroelectric film and electrodesconstituting the ferroelectric capacitor may be changed in accordancewith the specification of the ferroelectric capacitor.

The structures of the embodiments are not limited to ferroelectricmemories in which TC parallel units are connected in series. Rather, thepresent invention can be applied to memories of various types thatincorporate ferroelectric capacitors. The invention can be applied alsoto semiconductor devices, such as MEMSs, which use ferroelectriccapacitors as functional elements.

Additional advantages and modifications will readily occur to thoseskilled in the art. Therefore, the invention in its broader aspects isnot limited to the specific details and representative embodiments shownand described herein. Accordingly, various modifications may be madewithout departing from the spirit or scope of the general inventiveconcept as defined by the appended claims and their equivalents.

1. A semiconductor device comprising: a substrate; and a ferroelectriccapacitor provided on the substrate and fabricated by forming a lowerelectrode, a ferroelectric film and a mask-material film on a part ofthe substrate, by making an opening in the mask-material film and byburying the upper electrode in the opening.
 2. The semiconductor deviceaccording to claim 1, wherein the substrate is a semiconductorsubstrate.
 3. The semiconductor device according to claim 2, furthercomprising: a switching transistor provided on the substrate, and aninterlayer insulating film provided on the substrate, covering thetransistor, and in which the ferroelectric capacitor is provided on theinterlayer insulating film.
 4. The semiconductor device according toclaim 1, wherein the mask-material film is made of alumina (Al₂O₃),zirconium oxide (ZrO₂), aluminium silicon oxide (AlSiO), silicon oxide(SiO₂), titanium oxide (TiO₂) or may be a multi-layer structure composedof films of these oxides.
 5. The semiconductor device according to claim1, wherein the sidewalls of the lower electrode and the sidewalls of theferroelectric film have surfaces which line on lines extending in thesidewalls surfaces of the mask-material film.
 6. The semiconductordevice according to claim 1, wherein that part of the ferroelectricfilm, which contacts the upper electrode, is 1 nm or more thinner thanthe other part.
 7. A semiconductor device comprising: a substrate; aferroelectric capacitor provided on the substrate and comprising a lowerelectrode, an upper electrode and a ferroelectric film interposedbetween the upper and lower electrodes, said upper electrode beingprovided in a region inner of a peripheral region of the ferroelectricfilm; and a mask-material film provided on the ferroelectric film andsurrounding the peripheral region of the upper electrode.
 8. Thesemiconductor device according to claim 7, wherein the substrate is asemiconductor substrate.
 9. The semiconductor device according to claim8, further comprising: a switching transistor provided on the substrate,and an interlayer insulating film provided on the substrate, coveringthe transistor, and in which the ferroelectric capacitor is provided onthe interlayer insulating film.
 10. The semiconductor device accordingto claim 7, wherein the mask-material film is made of alumina (Al₂O₃),zirconium oxide (ZrO₂), aluminium silicon oxide (AlSiO), silicon oxide(SiO₂), titanium oxide (TiO₂) or may be a multi-layer structure composedof films of these oxides.
 11. The semiconductor device according toclaim 7, wherein the sidewalls of the lower electrode and the sidewallsof the ferroelectric film have surfaces which lie on lines extending inthe sidewalls surfaces of the mask-material film.
 12. The semiconductordevice according to claim 7, wherein that part of the ferroelectricfilm, which contacts the upper electrode, is 1 nm or more thinner thanthe other part.